o -Oxazolinyl- and o -Thiazolinylphenol as Antennae in Luminescent Eu III and Tb III Complexes (original) (raw)
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Polyhedron, 2006
Two new Eu(III) complexes featuring 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate (hfac) and a rigid Lewis base ligand 2,4,6-tri(2-pyridyl)-1,3,5-triazine (tptz), ½EuðhfacÞ 2 ðH 2 OÞðEtOHÞðtptzÞ½CF 3 CO 2 À (1) and Eu(hfac) 3 (tptz) (2), were synthesized. Their structures were established by single crystal X-ray diffraction. The europium ion in each of these complexes is nona-coordinate with six oxygen and three nitrogen atoms forming a coordination polyhedron best describable as a monocapped square antiprism. The difference in the composition and structure between these two complexes is caused by simply reversing the order of ligand (hfac and tptz) addition during the complex synthesis, and is rationalized in terms of the structural and electronic properties of the ligands and the overall steric bulk of the coordination sphere. Both complexes display characteristic Eu(III)-originated red emission upon UV excitation. The high quantum yields observed, 52% (1) and 60% (2), are rationalized in terms of the strong absorptions of both hfac and tptz ligands near the excitation wavelength (295 nm), an interpretation consistent with the well-established mechanism of ligand-mediated energy transfer for lanthanide-based light emission.
Polyhedron, 2006
Europium complexes presenting general formulas [Eu(ACIND) 3 (H 2 O) 2 ] and [Eu(ACIND) 3 (TPPO) 2 ] have been synthesized and characterized. In these formulas ACIND is stands for the ligands 2-acetyl-1,3-indandionate (AIND), 2-isovaleryl-1,3-indandionate (ISOV-IND) or 2-benzyl-1,3-indandionate (BIND). The [Eu(ISOVIND) 3 (H 2 O)(EtOH)] complex was also prepared and its structure determined by single crystal X-ray analysis, showing that this complex crystallize in a monoclinic space group P2 1 /n with the water molecules bridging through the hydrogen bond. The Eu(III) ion is eight-coordinate in a bicapped trigonal prismatic geometry defined by the oxygen donor atoms with a site of symmetry close to C 2m . Isovaleryl groups in the ISOVIND molecules in the structure are disordered over two positions of the europium complex. Carbon atoms in ethanol molecule are disordered by the thermal vibration. Photoluminescence properties of these complexes in solid state were investigated both experimentally and theoretically, suggesting an efficient ligandto-metal intramolecular energy transfer process.
Chemical Papers, 2017
We report the synthesis of a novel type of bidentate chiral ligand which structurally derives from the association of a 1,2,3-triazole ring with a chiral oxazoline. Yttrium and lanthanide nitrato-complexes of the new triazolyl-oxazoline ligand were prepared and characterized. The coordination mode of the ligand was ascertained by means of DFT calculations. Trivalent europium and terbium derivatives resulted appreciably photoluminescent upon excitation with UV light, showing the typical 5 D 0 ? 7 F J and 5 D 4 ? 7 F J emissions, respectively. These species were successfully used for the preparation of luminescent-doped polymeric materials.
Molecules, 2021
New antenna ligand, 2-(phenylethynyl)-1,10-phenanthroline (PEP), and its luminescent Eu (III) complexes, Eu(PEP)2Cl3 and Eu(PEP)2(NO3)3, are synthesized and characterized. The synthetic procedure applied is based on reacting of europium salts with ligand in hot acetonitrile solutions in molar ratio 1 to 2. The structure of the complexes is refined by X-ray diffraction based on the single crystals obtained. The compounds [Eu(PEP)2Cl3]·2CH3CN and [Eu(PEP)2(NO3)3]∙2CH3CN crystalize in monoclinic space group P21/n and P21/c, respectively, with two acetonitrile solvent molecules. Intra- and inter-ligand π-π stacking interactions are present in solid stat and are realized between the phenanthroline moieties, as well as between the substituents and the phenanthroline units. The optical properties of the complexes are investigated in solid state, acetonitrile and dichloromethane solution. Both compounds exhibit bright red luminescence caused by the organic ligand acting as antenna for sensi...
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Inorganic Chemistry Communications, 2012
Lanthanide complexes with ortho-phosphorylated phenolate ligands LnL 3 (Ln = Eu, Tb, Lu; HL 1 =2-di(p-tolyl) phosphorylphenol; HL 2 = 2-diphenylphosphoryl-4-ethylphenol) were synthesized for the first time and characterized by elemental analysis, FTIR, 1 H, 31 P NMR spectroscopy, LDI-TOF mass-spectrometry. The energy gap between the triplet energy level and the corresponding resonance level of a lanthanide ion ( 5 D 1 for Eu 3+ and 5 D 4 for Tb 3+ ) is optimal for luminescence sensitization of only terbium ions. Bright green photo-and electroluminescence of terbium complexes was demonstrated.
New europium(iii) complexes containing hybrid ligands with hard and soft complexation centres
New Journal of Chemistry, 2003
The terpyridine-phenylphosphine oxide ligands 2-4 and their Eu 3+ complexes have been synthesized and studied. In acetonitrile solutions at room temperature, the complexes show an absorption band in the 300-350 nm region, indicating that the terpy units are coordinated to the metal. In these conditions, the complexes show a metal-centred luminescence, indicative of an energy transfer from the terpy subunits to the Eu centre. The efficiency of such an energy transfer process drastically depends on the nature of the anions: a 20-fold increase of the luminescence intensity could be observed upon adding up to 3 equiv. of nitrate to a solution containing equimolar amounts of ligand 2 and Eu(OTf) 3 . In other solvents, such as methanol, DMF, and DMSO, the metal ion is coordinated through the P=O group; in these conditions almost no metal-centred luminescence can be observed, showing that the efficiency of the energy transfer process from uncoordinated terpy units is almost negligible. The translocation of the Eu ion from the terpy unit to the P=O group can also be performed on adding Zn 2+ ions; the luminescence typical of the lanthanide ion disappears, while the typical fluorescence of Zn-terpy complexes is observed.
Substituted Phenanthrolines as Antennae in Luminescent Eu III Complexes
European Journal of Inorganic Chemistry, 2013
Eight novel europium(III)-based coordination compounds with 1,10-phenanthroline (phen) ligands with a chloro, methoxy, ethoxy, cyano, carboxylic acid, methyl carboxylate, ethyl carboxylate, and amino substituent on the 2-position have been prepared in yields ranging from 43 to 89 %. Additionally, one lanthanum(III) coordination compound of 2-amino-1,10-phenanthroline has been isolated. All compounds have the general formula [Ln(L) 2 (NO 3) 3 ], except for the compound with the carboxylate ligand, which has the formula [Eu-(O 2 Cphen) 3 ]. Three of the Eu III complexes as well as the La III compound crystal structures have been determined, all of [a]
Inorganica Chimica Acta, 2007
A series of new neutral iridium(III) complexes containing strong-field ancillary ligands, [Ir(ppy) 2 (PPh 3 )L] (ppy = 2-phenylpyridine, PPh 3 = triphenylphosphine, L = NCS À , 1; N À 3 , 2; NCO À , 3), have been synthesized and fully characterized by 1 H NMR, IR, ESI mass spectral and elemental analysis. The crystal structure of 1 has been determined by X-ray analysis. The photoluminescence (PL) spectra of 1-3 show emission maxima at 477, 489 and 485 nm, respectively, corresponding to blue light-emitting of 1 and blue-green lightemitting of 2 and 3. PL quantum yields (PLQYs) of 1-3 are 0.39, 0.13 and 0.43, respectively.
Structural and photophysical studies of europium complexes containing triazole ligands
Inorganica Chimica Acta, 2012
Mono-and bistriazoles ligands have been used to prepare ternary mixed ligand europium(III) complexes in which the remaining ligands are dibenzoylmethane anions (DBM). The complexes were characterized by various measurements including single-crystal X-ray crystallography. Photophysical studies on both ligands and the complexes were carried out. The complexes show strong sharp red emissions in the solid state corresponding to 5 D 0 ? 7 F J (J = 0-3) with a 5 D 0 ? 7 F 2 (612-613 nm) transition as the most prominent one. It was shown that high thermal stability, luminescence intensity and quantum yield comparable or higher than those for the Eu(DBM) 3 Phen makes such complexes a promising material for OLED.